Experiment 2

Bioinorganic Coordination Chemistry: metalloporphyrins

Perhaps the most important class of metal-containing compounds in biological systems is

that comprised of complexes between metal ions and porphyrin ligands. Porphyrins are
macrocylic tetrapyrrole systems with conjugated double bonds and various groups attached to
the perimeter (see Figure 1). A porphyrin (PH2) can lose two protons to become a 2- anion (P2-).
It is the anionic form of the porphyrin that complexes with metal ions, usually in the +2
oxidation state, to form a metalloporphyrin complex (see Figure 1). A number of biologically
important molecules such as hemoglobin and myoglobin contain iron porphyrin moieties (see
Figure 2) .

A )

B )

Figure 1. (A) A general reaction showing the Bronstead acid properties of a porphyrin. (B) A
general reaction showing the formation of a metalloporphyrin.

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Figure 2. Protoheme IX, the prosthetic group for many important biologically important
molecules.

A group of compounds closely related to porphyrins are chlorins. The chlorin ring system
shown in Figure 3a is a porphyrin in which the double bond in one of the pyrrole rings has been
reduced. Chlorophyll is a magnesium complex of a chlorin. Chlorophyll a, shown in Figure 3b, is
one of the molecules used to trap the energy of photons in the photosynthetic process.

( A ) ( B )

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Figure 3. (A) The basic ring structure of a chlorin. (B) Chlorophyll a

Lewis Acids and Bases: Metalloporphyrins are Lewis acids. In this experiment you will study
adduct formation between either nickel or zinc tetraphenylporphyrin and a Lewis base such as
pyridine or imidazole in toluene or methylene chloride. In the adduct a coordinate covalent bond
is formed between the zinc ion in the metalloporphyrin and the nitrogen atom of the pyridine (or
imidazole). The formation of the adduct between NiTPP or ZnTPP and pyridine can be detected
using UV-vis spectroscopy.

Absorption spectra of porphyrins and metalloporphyrins: An intense absorption band (ε =

2-5 x 105) in the region of 400 nm is observed for porphyrins and metalloporphyrins. This band
is known as the Soret band. The position of the Soret band is both pH and solvent dependent.
The 500-700 nm region contains a series of bands. The number and relative intensities of
these bands is dependent on the pH and solvent. For most porphyrins in neutral solvents the
visible spectra consist of four bands whose intensities are generally at least an order of
magnitude less intense than the Soret band. (ε ~104). For most metalloporphyrins of divalent
metal ions (i.e. Zn2+) the visible spectrum consists of two bands. Upon coordination of zinc
porphyrins with Lewis bases there is, at least in most cases, a shift of the absorption bands to
longer wavelengths. A shift of absorption bands to longer wavelengths is often referred to as a
red shift.

Synthesis of meso-Tetraphenylporphyrin, C44H30N4 (H2TPP): Heat 40 mL of propanoic

(propionic) acid to reflux. Once the propanoic acid begins to reflux vigorously, add a mixture of
1.65 mL (15.75 mmol) of benzaldehyde and 1.0 mL (14.4 mmol) of pyrrole by slowly pouring
this solution down the reflux condenser. Rinse the pyrrole and benzaldehyde down the condenser
with 10 mL of propanoic acid. Reflux the solution for 30 min and allow the flask to cool for a
few minutes. Filter the dark brown mixture through a medium porosity frit. Rinse the mixture
with a few mL of methanol until the washings are clear and purple crystals remain on the frit.
Allow the crystals to dry by pulling air through them for several minutes.

Synthesis of (Tetraphenylporphyrinato)zinc(II), ZnTPP: Add 20 mL of N,N-

dimethylformamide (DMF) to 0.1 g of H2TPP (0.16 mmol) and stir the mixture (it is not
necessary for all of the H2TPP to dissolve). To the dark purple solution add 0.11 g (0.80 mmol)
of ZnCl2. Reflux the solution for 30 min. Cool to room temperature in an ice bath (5-10 min) and
add 50 mL of distilled water and return to the ice bath for an additional 5-10 min. to precipitate
the product. Filter the reaction mixture through a medium porosity frit and wash with distilled
water. Allow the crystals to air-dry until next week.

Synthesis of (Tetraphenylporphyrinato)nickel(II), The synthesis of NiTPP uses 0.1 g of

anhydrous nickel(II) chloride but is otherwise identical to the synthesis of ZnTPP.

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Characterization of H2TPP and NiTPP or ZnTPP:

1. Obtain the visible spectra (475-700 nm) of toluene solutions (~ 0.1 mg/mL) of H 2(TPP) and
either NiTPP or ZnTPP.

2. Prepare another solution (~0.1 mg/mL) of either NiTPP or ZnTPP in 1.2 M pyridine with
toluene as a solvent and obtain its visible spectrum (475-700 nm).
Instruction for calculating the percent chlorin in your crude H2TPP:

Absorption spectrum of pure meso-H2TPP in benzene λ max in nm ε values are given in

parentheses 485 (3400), 515 (18700), 548 (8100), 592 (5300), 647 (3400).
Absorption spectrum of pure chlorin in benzene λ max 518 (15,000), 543 (10,800), 600 (5800),
654 (41,700).
The absorbance at 485 nm is due entirely to the H2TPP. The ε values for pure H2TPP are
identical at 485 and 650 nm.

1. Record the spectrum of your H2TPP in toluene.

2. Subtract the absorbance of your crude porphyrin solution at 485 nm from the absorbance of
your solution at 650 nm. The difference is the absorbance due to chlorin.
3. Multiply the chlorin absorbance/porphyrin absorbance ratio by the ε value of pure meso-
H2TPP at 650 nm. This value is the ε value for the chlorin in your sample.
4. Multiply the ε chlorin in sample/ε pure chlorin by 100 % to calculate the percent chlorin in
you’re your crude porphyrin.

Report: Your report should include your % yield for your H2TPP and ZnTPP syntheses, the
absorption spectra of H2TPP, NiTPP or ZnTPP, NiTPP or ZnTPP (in pyridine/toluene and the %
chlorin in your crude H2TPP.

sources: Professor Glenn C. Vogel Ithaca College

Marsh, d.F.; Mink, L.M. J. Chem. Ed. 1996, 73, 1188.

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